ABSTRACT Aqueous zinc‑iodine (Zn‐I 2 ) batteries demonstrate significant potential for large‑scale energy storage, yet their practical application remains hindered by polyiodide shuttling at the cathode and uncontrolled Zn dendrite growth at the anode. In this work, an asymmetric twist molecule (ATM) was designed, which disrupts the equilibrium of molecular charge distribution and spatial steric effects. The rigid twist backbone locks the amino and carboxyl groups in a fixed orientation, generating a permanent molecular dipole that creates a stable local electrostatic field. This field adsorbs iodide ions, suppressing iodine hydrolysis and preventing polyiodide migration. Meanwhile, the oriented local electric field homogenizes the Zn 2+ flux and mitigates dendrite formation at the Zn anode, enabling uniform Zn deposition. Consequently, experimental results demonstrate that the Zn‐I 2 battery delivers a reversible capacity of 235 mAh g −1 under a high loading of 7.3 mg cm −2 . Furthermore, the ATM containing Zn//Zn symmetric cell exhibits an ultralong cycling lifespan exceeding 6100 h at 1 mA cm −2 . This study proposes a feasible technical pathway for constructing highly stable aqueous Zn‐I 2 batteries through the concept of asymmetric twist molecular design.

Solid-state lithium metal batteries hold great prospect for advanced energy storage devices with high energy density and safety. As one of the promising solid electrolytes, poly(vinylidene fluoride) (PVDF)-based electrolytes draw extensive attention due to their desired mechanical robustness, remarkable electrochemical stability and great processability. However, the inferior ionic conductivity and severe interfacial reactions still present obstacles to the practical applications of PVDF-based electrolytes. Recent progress has indicated that rational modification of PVDF-based electrolytes is a promising strategy to promote ionic conduction and enhance interfacial stability. In this review, the fundamental properties of PVDF-based electrolytes are first introduced and discussed, with the emphasis on ion transport behaviors and interfacial chemistry with both Li metal anodes and cathodes. Subsequently, the latest significant advances in PVDF-based electrolytes for promoting ionic conduction are comprehensively reviewed. Moreover, regulatory strategies for optimizing electrode/electrolyte interfaces are systematically summarized and discussed. Finally, this review highlights the current challenges and outlines prospective directions to develop advanced PVDF-based electrolytes with excellent all-around properties for practical applications.

Aqueous ammonium-ion batteries (AAIBs) have attracted considerable interest as promising candidates for large-scale energy storage systems due to their low cost, intrinsic safety, and environmental friendliness. Distinct from conventional spherical metal ions, NH4+ possesses a tetrahedral geometry and a strong tendency to form hydrogen bonds with surrounding species, which facilitates fast ion transport. At the same time, these features impose specific requirements on the chemical environments of the electrolyte, interface, and host frameworks. Although various inorganic materials have been explored for AAIBs, issues such as structural instability, dissolution, and limited cycling durability remain challenging, partly due to the fixed coordination environments of inorganic lattices. Organic materials offer distinct advantages arising from their molecular-level tunability, diverse functional groups, and flexible structural frameworks, enabling favorable interactions with NH4+ through hydrogen bonding, coordination, and electronic delocalization. These features allow organic components to effectively regulate the thermodynamics and kinetics of ammonium-ion storage and transport. This review systematically examines the functional roles of organic materials in AAIBs, highlighting how molecular structures and interaction mechanisms translate into electrochemical performance, and summarizes recent advances in their applications as electrode materials, hybrid electrode architectures, and electrolyte components. Furthermore, the current challenges and future research directions are discussed to guide the development of high-performance AAIBs.

ABSTRACT Hydrogels are widely applied in various fields, including energy storage and flexible electronics. However, their mechanical properties often fail to meet the requirements for long‐term and repeated deformation and full recovery. Achieving simultaneous improvement in the strength, toughness, and elasticity of hydrogels remains a significant challenge. Here, we report a nanoconfined polymerization strategy within the well‐designed, fully delaminated nanoscale covalent organic frameworks (nCOFs) that overcomes these trade‐offs. This approach yields hydrogels with an order increase in strength (from 0.3 to 3.2 MPa), a two orders enhancement in toughness (from 7.5 to 186 MJ/m3) and fracture energy (from 0.8 to 14.7 kJ m−2), and a very low‐hysteresis (∼93% energy recovery) recoverable deformation even after 2000% strain in the 100 cycles. The dense entanglements provide high strength and toughness, and nanochannel‐threaded crosslinking enables large elastic deformation. Furthermore, their robust architecture affords a fivefold improvement in puncture resistance, enabling application as dendrite‐inhibiting and durable quasi‐solid‐state Zn‐ion electrolytes. This bottom‐up toughening strategy based on the nano‐reactor nCOF structural design could guide the development of next‐generation tough hydrogels for applications such as flexible energy devices and related fields.

Gallium nitride (GaN) shows great promise for electrochemical energy storage owing to its robust structural and chemical stability. Wide-temperature adaptability has become an essential evaluation indicator for next-generation energy storage devices working under extreme hot and cold environments. In this work, heavily doped porous GaN crystals are composited with MoS2 to form a Type-II van der Waals heterostructure. Combined with a LiCl water-in-salt electrolyte, the as-fabricated electrode delivers outstanding capacitive performance across a wide temperature range of −22–70 °C. Comparative experiments with gradient MoS2 loadings verify that electronic modulation at the heterointerface dominates performance enhancement, with a larger contribution than the additional active sites provided by MoS2 itself. The heterojunction-induced built-in electric field facilitates interfacial charge redistribution and reduces ion adsorption barriers, while hierarchical pore channels facilitate full electrolyte infiltration and fast ion migration. The optimal GaN/MoS2 electrode achieves an ultrahigh areal capacitance of 5067 mF·cm−2 at 5 mA·cm−2. The assembled symmetric supercapacitor delivers a maximum power density of 22.5 mW·cm−2 and an energy density of 71.1 μWh·cm−2 at 70 °C. This heterostructure construction strategy provides an effective route to fabricate GaN-based hierarchical electrodes toward practical full-temperature-range energy storage.

Polymer electrolytes (PEs), valued for their superior safety and processability in lithium metal batteries (LMBs), often face trade-offs between ionic conductivity and mechanical strength, along with interfacial instability. Herein, we report a molecular programming strategy that encodes desired functionalities directly into the PEs network. This strategy is executed by programming urethane groups as functional units into the network via an in situ programmed click reaction, wherein trace water and Lewis acid salts in the electrolyte mediate the click crosslinking of glycidyl methacrylate with 2-isocyanatoethyl methacrylate. In this programming, each urethane group concurrently serves as a covalent crosslinker for mechanical integrity and a dynamic unit for self-healing, thereby constructing a topological terpolymer framework. Additionally, these units participate in reshaping the ion transport environment, guiding the formation of a mechanochemically stable interphase layer. Consequently, this programmed electrolyte exhibits a surface Young's modulus as high as 3.7 GPa, and excellent ionic conductivity. The 1 Ah pouch cell retains 96.39% capacity after 500 cycles. This work establishes a programming paradigm for PEs, advancing the application of high-performance PEs in LMBs.

Polymer-based solid-state electrolytes with high flexibility and excellent processability present great prospects in all-solid-state lithium batteries. However, when encountering interface stability problems, the application of polymer-based solid-state electrolytes in allsolid-state lithium batteries is puzzling. In this work, we proposed a lithium crosslinking strategy to regulate the interfacial chemistry by tailoring an effective Li2O-rich solid electrolyte interphase layer attributed to introducing 15-crown-5 into the polymer matrix. Specifically, crosslinking the 15-crown-5 with Li+ in polymer-based solid-state electrolytes boosts the Li+ transport by weakening the coordination between Li+ and polymer chains. The crosslinked 15-crown-5 moves along with the Li+ to the anode and decomposes to form the Li2O-rich solid electrolyte interphase with faster Li+ diffusion kinetics, resulting in uniform lithium deposition and suppressing the dendrite penetration. Therefore, the symmetric Li-Li cell could stably maintain cycling over 1100 h without shortcircuiting. The LiFePO4∥Li full battery presents high retention of capacity (92.75

Poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based polymer electrolytes demonstrate significant potential for quasi-solid-state lithium metal batteries (QSSLMBs) owing to their exceptional room-temperature ionic conductivity. However, the uneven distribution of DMF solvent induces the development of nonuniform solvation structures within electrolytes. Moreover, the different solvation structures exhibit pronounced discrepancies in interfacial stability and ionic transport kinetics, resulting in sluggish ion transport and electrochemically unstable electrode-electrolyte interfaces. Herein, we report precise modulation of the solvation structure through intermolecular interaction between the ZIF-67 filler and the DMF solvent. The corresponding Co-N site in ZIF-67 specifically adsorbs the C═O group of the DMF solvent, driving the formation of a uniform contact ion pair (CIP)-dominated solvation structure, which simultaneously enhances ionic transport kinetics and stabilizes electrode-electrolyte interfaces. The optimized electrolyte endows Li//Li symmetric cells with ultralong cycling stability exceeding 5600 h at 0.1 mA cm-2, while Li//NCM811 full cells achieve excellent cycling stability for more than 1600 cycles at 4.3 V and 200 cycles at 4.5 V, respectively. This interfacial modulation paradigm provides fundamental guidance for developing high-voltage QSSLMBs (4.5 V) through precise solvation structure engineering.

Quasi-solid-state electrolytes (QSSEs) represent a promising strategy to address the interfacial incompatibility of inorganic solid electrolytes and the sluggish ion kinetics of polymer solid electrolytes. Conventional approaches employ porous matrices to host minimal liquid electrolytes, yet remain constrained by limited ion transport enhancement and neglected electrode-electrolyte interfacial dynamics, resulting in poor electrochemical performance under high-rate and high-loading conditions. Hence, this work develops a novel quasi-solid electrolyte through molecular engineering of metal-organic frameworks (UiO-66-Br electrolyte), which modulates Li+-TFSI- interactions to establish solvent-separated ion pairs (SSIPs)-dominated solvation structures. This yields a high ionic conductivity of 1.58 mS cm(-1) at 20 degrees C. Furthermore, the derived LiBr/LiF-rich solid-electrolyte interphase (SEI) enables ultrafast interfacial ion transport kinetics. Through synergistic promotion of bulk-interfaces ion transport kinetics, while the LFP|UiO-66-Br|Li cells demonstrate exceptional cycling stability, achieving approximate to 100% capacity retention after 2300 cycles at 5 C with negligible decay. Under high mass-loading conditions (>20 mg cm(-2)), which can maintain 95.1% capacity retention over 100 cycles. This molecular engineering strategy pioneers a new paradigm for designing high-performance quasi-solid-state lithium-metal batteries.

The aqueous preparation of Na3(VOPO4)2F cathode material with low cost and good structural stability has attracted extensive attention for advancing sodium-ion batteries (SIBs). However, the inclusive heterogeneous cations incorporated into the material lattice, dominated by coordination chemistry, are always overlooked. Herein, the embroiled NH4+ /H3O+ cations in the Na3(VOPO4)2F lattice have been first disclosed during aqueous co-precipitation. It involves the electrostatic interactions between hydrogen protons (NH4+ /H3O+) and electronegative oxygen atoms (V=O and V-O-P groups), which induces the terrible Na+-storage performance, as demonstrated by multiple characterizations. Followingly, the very-facile operation, i.e. heat treatment, has been raised to remove NH4 + /H3O+ cations and then achieved high-performance Na3(VOPO4)2F. Therefore, the Na3(VOPO4)2F||Na cell contributes to the significantly improved discharge capacity (129.7 mAh g-1) and voltage plateau from 3.63 to 3.87 V (vs. Na/Na+) at 0.2 C. The ultrahigh capacity retentions of 93.7% and 76.7% after 1000 and 3500 cycles at 1 and 20 Crates under 25 degrees C are harvested, respectively, as well as high/low-temperature performances and rate capability. Eventually, the as-assembled Na3(VOPO4)2F||hard carbon full-cell delivers excellent long-term cycling stability over 1000 cycles with 97.5% retention at 3 C. These emphasize the high-efficacy synthesis of Na3(VOPO4)2F and provide insights into the aqueous co-precipitation for the development of materials used in SIBs. (c) 2025 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Alluaudite-type Na2+2δFe2-δ(SO4)3, characterized by its cost-effectiveness and high operating voltage, has emerged as a prospective cathode material for sodium-ion batteries (SIBs). However, poor electronic conductivity and sluggish reaction kinetics hinder its practical application. In this study, we developed a low-strain spherical Na2.5Fe1.75(SO4)3@C@KB (NFS@C@KB) cathode, enclosed within highly conductive Ketjen Black (KB) using a scalable spray-drying method. In-situ X-ray diffraction analysis revealed that the nearly zero-volume strain originates from the synergistic effect of the dense spherical configuration and pearl-like KB branched chains, effectively enhancing the structural stability and prolonging the cycle life. Moreover, the interconnected KB network establishes a continuous electron transport pathway, thereby improving the electronic conductivity. The optimized NFS@C@KB cathode delivered a capacity of 75 mAh g-1 at 5C and exhibited remarkable cycling stability over 4000 cycles. Even under the extreme condition of -20 °C, it retained a discharge capacity of 63 mAh g-1 at a rate of 1C. Consequently, the combination of a low-strain structure and outstanding electrochemical performance is expected to stimulate further exploration of iron-based sulfate cathodes and promote the development of rechargeable SIBs for energy storage applications.

Metal-organic frameworks have aroused growing interest in the research of energy conversion and storage. However, their specific configuration, especially the coordination environment of metal active sites, has not been well designed. Their role in regulating the structural reconstruction of pre-electrocatalysts remains ambiguous. Herein, this work reports a dual-ligand strategy to design a Ni-MOF with asymmetric Ni-O coordination, named Ni-BDC-DOBDC, which occupies unsaturated Ni sites and strengthens Ni-O bonds. As inspected by X-ray absorption near edge structure as well as a series of in situ and ex situ characterizations, this special Ni-O coordination contributes to Ov-NiOOH with rich oxygen vacancies during fast self-reconstruction at a lower potential. Moreover, theoretical results reveal that Ni sites in Ov-NiOOH occupy a higher d-band center, a lower adsorption energy barrier, and a more electronic negative surface in the oxygen evolution reaction, leading to good electrocatalytic performance. Overall, Ni-BDC-DOBDC catalysts exhibit a low overpotential of 202 mV at 10 mA cm-2 and outstanding stability within 240 h. The insights in this work pave the way for high-performance MOF-based catalysts by regulating their self-reconstruction kinetics through a new aspect of asymmetric ligand engineering.

The development of high-energy-density all-solid-state lithium batteries (ASSLBs) hinges critically on the design of advanced composite cathode components. While significant progress has been made in optimizing solid electrolytes as separators, the advancement of catholytes-particularly those combining multi-electron pair redox activity, high ionic conductivity, and mechanical compressibility-remains underexplored. A key challenge in current composite cathodes is the non-negligible high loading of electro-inactive electrolytes, which drastically reduces the energy density of the ASSLBs. To address this limitation, we propose an alternative strategy to improve the energy density by using Li2.6Ti0.6Zr0.4Cl6 as an electro-active catholyte with multielectron pair. This material exhibits exceptional ionic conductivity (1.39 mS cm-1 at 25 degrees C) while simultaneously delivering a highly reversible specific capacity of approximately 90.62 mAh g-1. Aliovalent Ti substitution enhances ionic conductivity through a structural transition from high-symmetry to low-symmetry space groups, coupled with a crystallinity strengthening effect. Moreover, the composite cathode of Li2.6Ti0.6Zr0.4Cl6 and LiFePO4 reveals an impressive initial discharge capacity of 258.97 mAh g-1LFP. This work introduces a new type of functional electro-active catholyte, significantly enhancing the energy density and cost-effectiveness of ASSLBs, opening new avenues for the development of next-generation solid-state battery technologies.

In situ polymerized poly(1,3-dioxolane) (PDOL) electrolytes endow excellent interfacial contact and satisfactory compatibility in lithium metal batteries (LMBs). However, their limited oxidative stability hinders compatibility with high-voltage cathodes. Herein, an effective molecular weight modulation-induced strategy via multifunctional subnanowires (SNWs) was proposed to realize the superior oxidative stability of PDOL electrolytes with narrow molecular weight distribution (MWD). Specifically, the ring-opening polymerization of DOL was promoted by oxygen vacancies (Ov) on SNWs, which enhanced the monomer conversion rate. Simultaneously, the polymerization speed during the in situ process was regulated by the weak adsorption of monomers induced by protonated oleylamine (PO). Furthermore, the dual Lewis acid sites (Ov and PO) of the SNWs facilitate lithium salt dissociation, releasing more movable Li+ for transport. Thus, the SNWs-induced polymerized PDOL electrolytes with an MWD of 1.42 exhibit remarkable oxidative stability exceeding 5.1 V while achieving a lithium-ion transference number of 0.81. Consequently, the assembled NCM811||Li cells maintain a stable operation for 100 cycles at 4.5 V with a capacity retention rate of 89.2%. This research first modulates the MWD of in situ polymerized PDOL electrolytes using subnanowires to enhance their oxidative ability, presenting a unique strategy to inspire the development of high-performance LMBs.

Iron-based mixed phosphates are considered as promising cathode materials for sodium-ion batteries (SIBs) due to their low cost, non-toxicity, and high structural stability. However, their electrochemical performance is limited by poor electronic conductivity and sluggish ion diffusion. In this study, Na4Fe3(PO4)2(P2O7) with porous coral-like S-doped carbon (NFPP-U0.5

Composite solid-state electrolytes have received widespread attention due to their excellent comprehensive performance. Herein, sub-1 nm Yb2O3-based polyoxometalates heterogeneous cluster chains (YOP) are designed to construct enrich and continuous Li+ interface pathways. The terminal oxygen in phosphomolybdic acid attracts local electrons from Yb in the heterogeneous structure, inducing electron rearrangement and strengthening the local positive charge of Yb3(+), which enhances interfacial interactions and promotes lithium salt dissociation. Then, the YOP cluster chains are grafted with polyether amine and uniformly dispersed in the PVDF-HFP matrix via hydrogen bonds, significantly increasing the organic-inorganic interface area. Under the effect of strong local charge, the beta-phase transformation of PVDF-HFP is induced for aligning dipoles of & horbar;CF2 & horbar; groups to optimize Li+ distribution and form continuous, oriented Li+ interface pathways. Consequently, the YOPSE exhibits high ionic conductivity (0.68 mS cm-1), a lithium-ion transference number of 0.62, and excellent cycling stability (98.5% capacity retention of LFP/Li batteries after 800 cycles at 2C). This study demonstrates the synergetic effects of hetero-structure nanomaterials and polymer matrix, providing insights into solid-state battery designs.

1,4-naphthoquinone (NQ) is anticipated to emerge as a promising electrode material for designing high-performance aqueous proton batteries (APBs), attributed to its high theoretical capacity and flexible designability. However, its high solubility and sluggish kinetics are not conducive to long-term cycling stability and high-rate capability. Herein, a unique molecular structure design strategy is proposed to construct effective p-pi conjugated structures by inducing the p-electrons in substituent groups and pi-electrons on naphthalene rings. Theoretical calculations and experimental results indicate that the p-pi conjugation effect of 2,3-dichloro-1,4-naphthoquinone (2Cl-NQ) and 1-hydroxy-1,4-naphthoquinone (1OH-NQ) greatly reduces molecular polarity and expands the pi-conjugate system, which endows them with minimal solubility and superior structural stability, thereby achieving excellent cycling stability with 99.53% and 98.62% capacity retention after 1800 cycles, respectively. Moreover, the p-pi conjugated structures induce a narrowed bandgap, improving electronic conductivity and redox kinetics, thereby significantly enhancing their rate capability. When coupling with perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) anode, the full battery of 2Cl-NQ//PTCDA exhibits a high specific capacity of 173 mAh g(-1) at 15 A g(-1), maintaining 73.2% capacity retention after 40 000 cycles and demonstrating exceptional cycling performance even at -20 degrees C. This work provides valuable insights and guidance for designing high-performance energy storage materials for APBs.

Aqueous Zinc ion batteries (AZIBs) hold significant promise due to their inherent safety, cost-effectiveness and environmental friendliness. However, the instability of the electrode-electrolyte interface stems from highly active water molecules and intrinsic characteristics of electrodes. The active water molecules easily attack both the cathode and anode surfaces, leading to the dissolution and structural degradation in the cathode materials as well as corrosion and passivation of the anode surface. The single modification strategy aimed at one electrode interface is insufficient to enable the practical application of AZIBs. Therefore, it is essential to systematically deconstruct the bidirectional interface regulation strategies and analyze efficient pathways to simultaneously resolve issues of both electrodes. Based on the challenges of the dual electrode-electrolyte interfaces, this review focuses on electrolyte engineering (including additives, hydrogels, and eutectic systems), multi-functional separators (such as modified glass fiber and novel separators), and artificial interfacial layers (covering both anode and cathode protective layers). A more detailed evaluation of the mechanisms and strategies for enhancing both sides in AZIBs is systematically provided. Three types of regulation strategies are also outlined for bidirectional reduction of the active water-induced issues, which aim to achieve the highly efficient AZIBs through a concise categorization of different approaches.

Deep eutectic electrolytes (DEEs) are emerging as a highly promising class of next-generation electrolytes, poised to revolutionize the performance of safe sodium-ion batteries (SIBs). Nevertheless, a significant challenge hindering the progress of SIBs is the scarcity of suitable DEEs capable of harmonizing electrolyte conductivity, interfacial compatibility, and safety. In this study, we have engineered a DEE leveraging the synergistic interplay between Na-bonds and hydrogen bonds, achieved through the integration of N -methylacetamide (NMA) and sodium-difluoro(oxalato)borate (NaDFOB). The findings reveal that the distinctive interaction between the polar C═O group in NMA and Na + ions, coupled with hydrogen bonding with DFOB − anions, facilitates the formation of the DEE. The designed DEE demonstrates exceptional ionic conductivity (4.03 mS cm −1 at 25 °C), a high oxidation voltage (4.63 V versus Na + /Na), and nonflammability. The unique solvation structure markedly enhances the compatibility of the electrode–electrolyte interface, with the NVP||Na cell exhibiting outstanding cycling performance (86.8% retention after 7000 cycles at 5 C) and superior rate capability. Moreover, the DEEs exhibit robust performance at elevated temperatures (94.3% retention after 120 cycles with NVP||Na cell), and the full cell demonstrates significant enhancements in both cycle stability (90.7% retention after 300 cycles) and rate performance. The incorporation of amide-based eutectic electrolytes into SIBs infuses fresh vitality into electrolyte design, propelling the advancement of high-performance SIBs.